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CN1235629A - Heavy oils with improved properties and additive therefor - Google Patents

Heavy oils with improved properties and additive therefor Download PDF

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Publication number
CN1235629A
CN1235629A CN97199328A CN97199328A CN1235629A CN 1235629 A CN1235629 A CN 1235629A CN 97199328 A CN97199328 A CN 97199328A CN 97199328 A CN97199328 A CN 97199328A CN 1235629 A CN1235629 A CN 1235629A
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Prior art keywords
additive
acid
metal
carbon atoms
weight
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CN97199328A
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Inventor
G·赫泰尔
M·费尤斯泰尔
H·比斯特罗姆
G·理查兹
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Baikexin Co Ltd
Clariant Produkte Deutschland GmbH
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Baikexin Co Ltd
Clariant GmbH
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Publication of CN1235629A publication Critical patent/CN1235629A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1885—Carboxylic acids; metal salts thereof resin acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1888—Carboxylic acids; metal salts thereof tall oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

The additive described essentially comprises a selected alkoxylated fatty amine or fatty amine derivative and a special metal salt compound, preferably a metal soap. This additive for heavy oils effects a good emulsification or dispersion of asphaltenes and other higher-molecular weight compounds and, in addition, inter alia, increased storage stability, improved pumpability due to decreased viscosity of the oil and longer service lives of the filter systems. In addition, it also effects enhanced combustion of the heavy oils. The effective amount of additive in these oils is 2 to 2000 ppm. The oils described are suitable, in particular, as furnace fuel for industrial plants and power stations and as engine fuel for marine engines.

Description

The heavy oil of improved performance and the additive that is used for heavy oil
The heavy oil that the present invention relates to improve the additive of performance of heavy oil and contain this additive.
Heavy oil obtains in petroleum-type (crude oil) processing, and is for example resistates in normal atmosphere or very aerial distillation, thermo-cracking or catalytic cracking etc. of the course of processing.From the angle of chemistry, fuel that these are remaining or remaining power fuel (" C " number heavy fuel oil) are made up of paraffinic hydrocarbons, naphthenic hydrocarbon and the aromatic hydrocarbon of part macromolecular structure basically.This high molecular component is also referred to as bituminous matter, can not exist with the dissolved form, but can exist with discrete form more or less, causes many problems thus.Therefore, bituminous matter and similar other poorly soluble or insoluble compound (for example oxygen compound, nitrogen compound and sulphur compound) and ageing products can be isolated from oil phase in the presence of no effective dispersion agent, form undesirable especially two phase systems.In addition, in the presence of water, even only in the presence of moisture, can form slurry equally.In addition, all these macromolecular compounds in the heavy oil and composition have a negative impact to the combustion processes of oil, for example cause forming a large amount of carbon blacks.
Heavy oil, particularly exist with the form of mixtures of heavy fuel oil (HFO) (marine fuel oil) form and heavy fuel oil (HFO) and last running (Inter oil fuel), main in large quantities as the use of the fuel in full scale plant and the power station, and as the slow relatively particularly motor spirit use of marine engine of oil engine of burning.Therefore, in the prior art, various additives have been proposed to use, by using these additives can eliminate the unfavorable performance of described heavy fuel oil (HFO) and dynamic fuel oil, particularly form the formation of two phase systems, slurry and to the incendiary disadvantageous effect because of bituminous matter and other macromolecule component.
Therefore, FR-A-2172797 has described organic acid alkali formula molysite, the mixture that FR-A-2632966 has described ironic hydroxide and alkaline calcium soap as auxiliary agent to improve the burning of heavy oil.The US-A-4129589 suggestion uses the magnesium salts of high alkalinity and oil-soluble sulfonic acid as oil additives.Nearest disclosed EP-A-476196 has described a kind of mixture as oil additive, it mainly comprises (1) at least a oil soluble manganese carbonyl compound, the organic acid alkali metal salt of (2) at least a oil-soluble neutrality or alkalescence or alkaline earth salt and (3) at least a oil-soluble dispersant that is selected from this group of being made up of the succinimide class.In addition, equally also can mention US-A-5421993, it has described the derivative that uses oxyalkylated fatty amine and fatty amine inhibiter, demulsifying compound and the pour point reducer as crude oil.
The mixture that has been found that oxyalkylated fatty amine compound and organic metal salt now is effective especially additive for heavy oil, particularly with regard to emulsification and dispersed bitumens matter, slurry etc. and the oily aspects such as burning of improvement.
Additive of the present invention is that benchmark is formed a) 1 to 99 weight % by following component basically in its weight, preferred 20 to 80 weight %, at least a amine compound of formula I down of preferred especially 40 to 60 weight % Wherein n is 1,2,3 or 4, and A is a formula II to one of the group of (V)
Figure A9719932800062
Here R is C 6-C 22-alkyl, preferably C 6-C 18-alkyl, m are 2,3 and 4,
Preferably 2 or 3, x is 5 to 120 number, preferably 10 to 80, and R 1Be H, CH 3Or H and CH 3Random or the block arrangement of oxyalkylene group wherein, and b) 1 to 99 weight %, preferred 20 to 80 weight %, at least a oil soluble of preferred especially 40 to 60 weight % or the neutrality of oil-dispersing property or basic metal salt compound, this compound comprises the periodic table of elements first main group metal, second main group metal, the first subgroup metal, the second subgroup metal, fourth officer family metal, the 6th subgroup metal, the 8th subgroup metal or lanthanide series metal (rare earth metal) and have 8 to 40 carbon atoms in each case, the carboxylic acid of the alkyl of preferred 12 to 30 carbon atoms, sulfonic acid, phosphate ester acid or acidic sulfate are as acidic components.
Components of additives of the present invention is the amine compound of formula I a).These alkoxylated alphatic amine and fatty amine derivative prepare according to conventional alkoxylating method, and promptly according to the group A in the formula I, the oxyethane of amine and x mole reacts (R separately 1Be that H and polyalkylene oxide groups are made up of ethylene oxide unit), perhaps the propylene oxide of amine and x mole reacts (R separately 1Be CH 3Form by propylene oxide units with polyalkylene oxide groups), perhaps the oxyethane of amine and x mole and propylene oxide are simultaneously or first afterreaction (R 1Be H and CH 3, polyalkylene oxide groups by random existence or form with ethylene oxide unit and propylene oxide units that block form exists).This reaction under the condition of secluding air, in the existence of alkalescence or acid alkoxylating catalyst or not, is carried out under 100 to 180 ℃ temperature usually.Preferred ingredient is the amine compound of following formula VI a) Wherein n is 1,2,3 or 4, and A is a formula II defined above to one of the group of (V), and a is 5 to 30 number, preferably 8 to 20, b is 5 to 50 number, preferably 10 to 30 and c be 0 to 40 number, preferably 0 to 20.
The amine compound of formula VI and its preparation method are described in detail among the above mentioned US-A-5421993, and the document is incorporated herein for your guidance.They be add alkali for example under the situation of alkali metal hydroxide by at first using oxyethane, use the above-mentioned formula II of propylene oxide alkoxylate to the amine of (V) to obtain then.This reaction is preferably being carried out in multistep is rapid under 100 to 160 ℃ the temperature.The usage quantity of catalyzer/alkali is in employed raw material amine 0.5 to 3.0 weight % normally.The oxyethane of every mole of raw material amine and the molar weight of propylene oxide are corresponding to value a and the b and the value c of regulation.Detailed content is referring to the US-A-5421993 that mentions.Provide the amine compound (a that is suitable as component formula I a) in the following explanation 1To a 6) example:
Formula I
Compound ???A ???????????R ????a ????b ????c
???a 1???a 2???a 3???a 4???a 5???a 6 Ⅱ Ⅲ Ⅴ Ⅳ Ⅲ Ⅲ C 14-C 18The unsaturated C of-alkyl 14-C 18The unsaturated C of-alkyl 14-C 18The unsaturated C of-alkyl 14-C 18The unsaturated C of-alkyl 14-C 18The unsaturated C of-alkyl 14-C 18-alkyl is unsaturated ????22 ????6 ????22 ????22 ????12 ????12 ????33 ????9 ????33 ????33 ????28 ????28 ????0 ????0 ????0 ????0 ????25 ????15
Components b) preferred metal is basic metal or alkaline-earth metal (periodic table of elements first and second main groups) in the metal salt compound, copper or silver (first subgroup), zinc or cadmium (second subgroup), titanium or zirconium (fourth officer family), molybdenum, chromium or tungsten (the 6th subgroup), iron, cobalt and nickel (the 8th subgroup) and lanthanum, cerium or ytterbium (group of the lanthanides).Particularly preferred metal is a basic metal, for example barium, beryllium, calcium or magnesium, copper, zinc, zirconium, molybdenum, iron, nickel, cerium or ytterbium.
Components b) preferred acid is to have 8 to 40 carbon atoms, the aliphatic carboxylic acid of preferred 12 to 30 carbon atoms in the metal salt compound.Aliphatic group can be a straight or branched, and is saturated or undersaturated.Aliphatic carboxylic acid preferably has 8 to 40 carbon atoms, the lipid acid of preferred 12 to 30 carbon atoms.Aliphatic carboxylic acid and lipid acid can be synthetic or natural, they can with self or exist with the form of mixtures of two kinds or multiple acid.The example that can mention is sad, capric acid, laurostearic acid (lauric acid), TETRADECONIC ACID (tetradecanoic acid), palmitic acid (palmitinic acid), stearic acid (stearic acid), 20 acid (eicosanoic acid), docosoic acid (mountain Yu acid), dodecenoic acid (lauroleic acid), tetradecenoic acid (myristoleic acid), hexadecylenic acid (physetoleic acid), octadecenoic acid (oleic acid), 12-isorpcinoleic acid (ricinolic acid), octadecadienoic acid (linolic acid) and punicic acid (linolenic acid) and cocoanut fatty acid, tallow fatty acid, palm-kernel resin acid etc.
Except that described (simply) lipid acid, dimer (fatty acid) yl equally also is preferred acid constituents.These dimer (fatty acid) yls are lipid acid R wherein of formula (VII) 2Be divalent hydrocarbyl mission (so R with 34 carbon atoms 2Be to contain the group of 34 carbon atoms and be that the total that forms in the dimerization reaction of the unsaturated fatty acids that contains 18 carbon atoms produces when having the di-carboxylic acid of 36 carbon atoms).
As everyone knows, they are by unsaturated C 18(dimerization reaction is interpreted as that two identical molecules are combined into new molecule, dipolymer by addition reaction) of the dimerization reaction preparation of lipid acid such as oleic acid, linolic acid, linolenic acid or tallow fatty acid.C 18The dimerization reaction of lipid acid is normally at 150 to 250 ℃, under preferred 180 to the 230 ℃ temperature, carries out under the dimerization reaction catalyzer having or do not have.The dicarboxylic acid that is obtained (being binary lipid acid) is the carboxylic acid of formula (VII), here R 2Be at C 18The divalence connection unit that forms in the lipid acid dimerization reaction, it carries two-COOH group and has 34 carbon atoms.R 2Acyclic (aliphatic series) or monocyclic or dicyclo (cyclic aliphatic) group that preferably have 34 carbon atoms.Acyclic group normally has branching (replacement) and single unsaturated extremely triple unsaturated alkyl groups of 34 carbon atoms.Cycloaliphatic groups has 1 to 3 two key usually equally.Normally two kinds or multiplely have a different R of structure of described preferred dimer (fatty acid) yls 2The mixture of the formula VII dicarboxylic acid of group.Usually the dicarboxylic acid mixture is more or less contained three polyglycerol fatty acids that form and do not remove in the distillation of product is handled in dimerization reaction.Similarly mixture also can be obtained by natural product, for example obtains in by pine extract production rosin.Below, illustrating some dimer (fatty acid) yls with molecular formula, the alkyl that wherein carries two-COOH group is acyclic, monocycle or bicyclic radicals:
Figure A9719932800091
Described dimer (fatty acid) yl commercial can trade(brand)name " lipid acid of dimerization " or " dimer (fatty acid) yl " obtain, the same just as described above, it contains three polyglycerol fatty acids more or less.
In addition, in components b) metal salt compound in preferred acid be in aliphatic series or aromatic group, to have 8 to 40 carbon atoms, the aliphatic series or the aromatic sulfonic acid of preferred 12 to 30 carbon atoms.Equally, aliphatic group can be straight chain or side chain, saturated or undersaturated.Aromatic sulfonic acid preferably has the alkyl that contains 12 to 30 carbon atoms or the Phenylsulfonic acid of alkenyl.In cited example, metallic soap is particularly preferred components b).
According to the present invention as components b) organic metal salt that uses can prepare by method described in the prior.Especially with reference to above mentioned FR-A-2172797, FR-A-2632966, US-A-4129589 and EP-A-476196, their disclosed contents are incorporated herein for your guidance to this.Should be oil soluble or be oil-dispersing property at least according to organic metal salt used in the present invention.In addition, they should be a kind of neutrality or alkaline product, and the latter is preferred.Term " alkalescence " as known, is represented the metal-salt that metal wherein exists with the stoichiometric quantity that is higher than organic acid residue.The pH value of the alkaline metal salt product that desire is used according to the present invention generally is 7.5 to 12, preferably 8 to 10.
Additive of the present invention be by under the situation of using or do not use solvent or dispersion agent with component a) and b) mix and prepare.Solvent that this class is suitable or dispersion agent are rudimentary or higher alcohols, for example ethanol, Virahol, butanols, decyl alcohol, dodecanol etc., rudimentary or senior dibasic alcohol and their monoalkyl or dialkyl ether be ethylene glycol, propylene glycol, glycol ether, TEG, four propylene glycol etc. for example, aliphatic series, aromatics or the cycloaliphatic hydrocarbon that is low to moderate medium boiling point be toluene, dimethylbenzene, petroleum naphtha etc. for example, light to medium heavy mineral oil, oil fraction, the mixture of natural or synthetic oil and their derivative and two kinds or multiple these solvents.These two kinds of components, amine compound and metal salt compound usually under atmospheric pressure with at 15 to 100 ℃, mix under preferred 20 to the 70 ℃ temperature.
Heavy oil of the present invention is characterised in that and comprises described additive.The significant quantity of additive can change in wide scope in heavy oil.Usually, heavy oil comprises 2 to 2000ppm additive, and preferred 100 to 1000ppm.
Additive of the present invention and the heavy oil that contains this additive have in demand characteristic, and this may mainly be owing to component of the present invention a) and b) the high synergy that is difficult to reckon with of combination produce.Therefore, this additive is present in the oil with the form of dissolving or high dispersive.Even in the oil with high-content bituminous matter and/or other high-molecular weight compounds, all these undissolved compositions are height emulsification and dispersive.Also be so under the situation of slurry, so can eliminate the formation of slurry to a great extent or reduce the formation of slurry at least significantly.In addition, additive of the present invention is very effective combustion enhancer.It guarantees the perfect combustion of heavy oil, reduces sooty simultaneously and forms.Therefore heavy oil of the present invention can satisfy the requirement that begins to mention with wonderful high level equally.Because above-mentioned effect; additive of the present invention produces the oil that has following advantageous property in addition especially: improved stability in storage (reducing the deposition of indissolvable component); the improved pumpability that obtains owing to low viscosity; prolong the working life of filtration system; improve the jet performance in the combustion unit; these performances additionally help making combustion optimization, and because the high effect of corrosion inhibition of additive has strengthened the corrosion protection effect of all devices.Therefore, heavy oil of the present invention mainly is used as the fuel in full scale plant and power station, and is used as the power fuel of marine engine equally.
By means of embodiment and comparative example the present invention is described in more detail now.-components of additives of the present invention is a):
Use the compound a in the table 1 1, a 3And a 5As component a).-components of additives b of the present invention):
The product b that use is described in detail below 1And b 2As components b).-product b 1:
Be used to prepare product b 1Lipid acid be by distillating Yatall MA (Talkoel) lipid acid
Distillate fat with the mixture of the resinous acid of the about 300 gram/moles of molecular weight is formed
Acid.
Batch of material:
FeCl 30.85 rise density 1.48g/cm 3
NH 30.785 rise density 0.91g/cm 3
0.22 liter of density 0.94g/cm of lipid acid 3
0.20 liter in water
0.80 liter of density 0.82g/cm of petroleum distillate 3
Under room temperature (15 to 30 ℃), make 0.85 liter of FeCl 3, 0.22 liter of fat
Acid, 0.20 premium on currency and 0.80 liter of petroleum distillate mix mutually.Under agitation,
In this mixture, add 0.785 liter of NH lentamente 3(thermopositive reaction).Stirring
This mixture heating up to 80 to 90 ℃, is obtained containing water and organic phase down.
Can finish the formation of phase by further adding petroleum distillate.Make this two-phase mutual
Separate (decantation), the centrifugation organic phase is to remove remaining water.Organic phase contains
Desirable ferric carboxylate compound.-product b 2:
Be used to prepare product b 2Lipid acid be the alkylbenzene of the about 322 gram/moles of molecular weight
Sulfonic acid.
Batch of material:
FeCl 344 milliliters of density 1.48g/cm 3
NH 334 milliliters of density 0.91g/cm 3
13 milliliters of density 1.06 g/cm of lipid acid 3
16 milliliters in water
84 milliliters of density 0.82g/cm of petroleum distillate 3
To be similar to product b 1Method prepare product b 2, alkyl benzene sulphonate (ABS) iron.
Additive of the present invention:
Embodiment 1a) 40 weight % compound as 1B) 60 weight % product b 1Organic molysite
Embodiment 2a) 60 weight % compound as 3B) 40 weight % product b 2Organic molysite
Embodiment 3a) 50 weight % compound as 5B) 50 weight % product b 1Organic molysite
The additive of the present invention of embodiment 1 to 3 by with component a) and b) mix and prepare (mixing temperature about 20 is to about 60 ℃).According to preferable methods, at first add component a), and under stirring and nitrogen atmosphere, be heated to about 40 to 50 ℃.Under said temperature and nitrogen atmosphere, be stirred into components b then), thus additive of the present invention obtained.If this mixture that the is cooled to room temperature not desirable viscosity of tool and/or observe is separated, these phenomenons can be eliminated by the organic solvent such as the petroleum distillate that add significant quantity so.-test additive of the present invention:
The additive of test implementation example 1 to 3 is to bitum dispersibility and heavy oil combustion
Improvement.In order to test bitum dispersibility, at first prepare asphaltenes
Solution.The solution of-preparation bituminous matter in toluene:
In order to prepare this solution, the Residual oil of asphaltenes is extracted, it is followingly to advance
Row.In first step, the Residual oil that makes about 30 grams in glass beaker is with about
300 milliliters ethyl acetate is mixed.Stirred this mixture 2 hours down at 40 ℃,
Left standstill then 24 hours, and then filtered by the simple bore strainer.In second step
In rapid, filtering residue is put into the conventional extracting cover that is used for Soxhlet extractron
In the pipe, reused about 300 milliliters ethyl acetate extraction about 2 hours, filter cake
In paraffinic hydrocarbons transfer to ethyl acetate mutually in.In third step, by means of about
300 milliliters pentane dissolves resin Composition by Soxhlet extractron equally.So
After, in the 4th step, by means of about 300 milliliters toluene extraction bituminous matter,
Thereby obtain the solution of desirable bituminous matter in toluene.-test additive of the present invention is to the improvement of pitch dispersibility:
Regulation according to ISO10307-1:1993 or ASTM D4370-32 (heat filtering)
Carry out this test.For this reason, at first make the bituminous matter of the about 10 weight % of 30 grams in first
Solution in the benzene mixes with 100 milliliters of pentanes.At room temperature, will be from embodiment
1,2 and 3 700ppm additive stir respectively into three parts of such bituminous matters-
In toluene/pentane solution.Then, according to these the three kinds of tests of described predetermined processing
Solution.The result: additive of the present invention satisfies test.-test additive of the present invention is to the improvement of heavy oil combustion:
According to VDI2066, the regulation of part 1 (VDI is a Verein Deutscher Ingenieure)
Carry out this test, wherein the usage quantity of embodiment 1,2 and 3 additive is
500ppm, 700ppm and 900ppm.The result: additive of the present invention satisfies examination
Test.
The comparative example 1 to 3
In comparative example 1 to 3, only use compound a respectively 1, a 3And b 1These three kinds of testing liquids are carried out the test method identical with embodiments of the invention.
Result: do not have a kind of testing liquid to satisfy the test that bituminous matter is dispersed and incendivity is improved.
Therefore, additive of the present invention has unexpected efficient aspect dispersion of heavy petroleum asphalt matter and the heavy oil combustion; This be by binder component a) and b) wonderful high synergy produce.Because the advantageous effect of this new additive, oil of the present invention have the performance of wishing especially when those use equally especially in full scale plant, power station and heavy-duty ship engine.

Claims (12)

1, being used to improve the additive of performance of heavy oil, is that benchmark is formed a) at least a amine compound of formula I down of 1 to 99 weight % by following component basically in the weight of additive
Figure A9719932800021
Wherein n is 1,2,3 or 4, and A is a formula II to one of the group of (V)
Here R is C 6-C 22-alkyl, m are 2,3 and 4, and x is 5 to 120 number, R 1Be H, CH 3Or H and CH 3Random or the block arrangement of oxyalkylene group wherein, and b) carboxylic acid, sulfonic acid, phosphate ester acid or acidic sulfate that the neutrality of at least a oil soluble of 1 to 99 weight % or oil-dispersing property or basic metal salt compound, this compound comprise the periodic table of elements first main group metal, second main group metal, the first subgroup metal, the second subgroup metal, fourth officer family metal, the 6th subgroup metal, the 8th subgroup metal or lanthanide series metal and have an alkyl of 8 to 40 carbon atoms in each case are as acidic components.
According to the additive of claim 1, it is characterized in that 2, component is the amine compound of following formula VI a)
Figure A9719932800031
Wherein n is 1,2,3 or 4, and A is a formula II defined above to one of the group of (V), and a is 5 to 30 number, and b is that 5 to 50 number and c are 0 to 40 numbers.
3, according to the additive of claim 1 or 2, it is characterized in that, components b) be metal salt compound, this metal salt compound comprise be selected from the metal in this group of forming by basic metal, alkaline-earth metal, copper, silver, zinc, cadmium, titanium, zirconium, molybdenum, chromium, tungsten, iron, cobalt, nickel, lanthanum, cerium or ytterbium and be selected from by the aliphatic carboxylic acid with 8 to 40 carbon atoms, have the dimer (fatty acid) yl of 36 carbon atoms and have the aliphatic series of 8 to 40 carbon atoms or this group that aromatic sulfonic acid is formed in acid.
4, according to the additive of claim 1 or 2, it is characterized in that, components b) is metal salt compound, wherein metal is alkaline-earth metal, copper, zinc, zirconium, molybdenum, iron, nickel, cerium or ytterbium, and acid constituents is lipid acid with 8 to 40 carbon atoms, have the dimer (fatty acid) yl of 36 carbon atoms or have the aliphatic series or the aromatic sulfonic acid of 8 to 40 carbon atoms.
5, according to one of claim 1 to 4 or multinomial additive, it is characterized in that, the component that it comprises 20 to 80 weight % a) and the components b of 20 to 80 weight %).
6, according to one of claim 1 to 4 or multinomial additive, it is characterized in that, the component that it comprises 40 to 60 weight % a) and the components b of 40 to 60 weight %).
7, according to one of claim 1 to 6 item or multinomial additive, it is characterized in that its pH value is 7.5 to 12.
8, heavy oil is characterized in that, it comprises the additive of the claim 1 of significant quantity.
9, heavy oil according to Claim 8 is characterized in that, it comprises 2 to 2000ppm additive.
10, the purposes of the additive of claim 1, it is as the combustion improver of emulsification and dispersion agent and heavy oil.
11, the purposes of the heavy oil of claim 8, it is as the fuel in full-scale plant and power station.
12, the purposes of the heavy oil of claim 8, it is as the power fuel of marine engine.
CN97199328A 1996-10-30 1997-10-21 Heavy oils with improved properties and additive therefor Pending CN1235629A (en)

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CN107429180A (en) * 2015-09-17 2017-12-01 李永瑞 Reduce the fuel additive of greenhouse gases, nitrogen oxides and particulate matter
CN109219649A (en) * 2016-03-18 2019-01-15 韩国化学研究院 By means of the heavy oil conversion method of asphalitine enhancement of dispersion

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CN107429180A (en) * 2015-09-17 2017-12-01 李永瑞 Reduce the fuel additive of greenhouse gases, nitrogen oxides and particulate matter
CN107429180B (en) * 2015-09-17 2020-08-25 李永瑞 Fuel additive for reducing greenhouse gases, nitrogen oxides and particulate matter
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